Process for the manufacture of alpha-iodoperfluoroalkanes and alpha, omega-diiodoperfluoroalkanes

ABSTRACT

The invention relates to a process for the manufacture of a-iodoperfluoroalkanes and α,ω-diiodoperfluoroalkanes of general formula: (1) A(C 2 F 4 ) n 1, wherein: A is selected from F, CF 3  and I and n is an integer equal to or higher than 1, with the proviso that, when A is F, n is an integer higher than 1 said process comprising heating a mixture [mixture (M1)] containing: —a compound selected from I 2 , CF 3 I, CF 3 CF 2 I and C 2 F 4 I 2 ; —TFE; —and CO 2  at definite temperatures and concentrations of CO 2 .

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to European application No. 14164336.1,filed on Apr. 11, 2014, the whole content of this application beingincorporated herein by reference for all purposes.

TECHNICAL FIELD

The present invention relates to a process for the manufacture ofα-iodoperfluoroalkanes and α,ω-diiodoperfluoroalkanes.

BACKGROUND ART

α-Iodoperfluoroalkanes and α,ω-diiodoperfluoroalkanes (herein afterotherwise respectively referred to as “I-telomers” and “I₂-telomers”)are useful reagents or intermediates in a variety of applications.

α-Iodoperfluoroalkanes having general formula F(CF₂)_(n)I, wherein n istypically an integer higher than 3, can be used, for example, asintermediates for the manufacture of surfactants, pesticides, electronicmaterials or pharmaceuticals.

α,ω-Diiodoperfluoroalkanes having formula I(C₂F₄)_(n)I (with n>1) suchas, for example, 1,4-diiodoperfluorobutane (C₄F₈I₂) and1,6-diiodoperfluorohexane (C₆F₁₂I₂), can be used as chain-transferagents in polymerization reactions, as intermediates for the manufactureof other chemicals, including bis-olefins, diacids, polymers or for themanufacture of coatings.

α-Iodoperfluoroalkanes are typically synthesized by means of atelomerization reaction of TFE with a α-iodoperfluoroalkane, preferablyCF₃I or CF₃CF₂I. Usually, the most common and industrially convenientway to initiate the reaction is the heating of the starting reactants,the heating temperature being proportional to the length of the desiredtelomers. The reaction can be carried out in the liquid phase at atemperature of at least 150° C. under pressure. Alternatively, thereaction can be carried out at a temperature as high as 450° C. eitherat atmospheric pressure, thereby providing only a monoaddition I-telomerin a single step of the reaction, or under pressure, thereby giving riseto a broad distribution of telomers. Methods for the synthesis ofI-telomers are disclosed, for instance, in U.S. Pat. No. 3,404,189 (FMCCORP) Jan. 10, 1968, U.S. Pat. No. 5,268,516 U.S. Pat. No. 5,268,516(ATOCHEM ELF SA) and WO 99/19248 (DU PONT) Apr. 22, 1999.

α,ω-Diiodoperfluoroalkanes are typically synthesized by means of aprocess comprising the reaction of tetrafluoroethylene (TFE) with iodinein the presence of different initiators, at different temperatures. Alsoin this case, on an industrial scale it is preferred to initiate thereaction by heating the reactants. TFE promptly reacts with iodine toprovide C₂F₄I₂, which is in equilibrium with TFE and iodine; C₂F₄I₂further reacts with TFE to provide higher-length telomers.

JP S51133206 (ASAHI GLASS CO LTD) Nov. 18, 1976 discloses a process forthe preparation of I₂-telomers of formula I(C₂F₄)_(n)I (n=2-4) bythermal decomposition of C₂F₄I₂. The telomerization reaction of TFE withC₂F₄I₂ is disclosed in TORTELLI, et al. Telomerization oftetrafluoroethylene and hexafluoropropene: synthesis ofdiiodoperfluoroalkanes. J. Fluorine Chem. 1990, vol. 47, p. 199-210.

Example 29 of WO 98/34967 A (THE UNIVERSITY OF NORTH CAROLINA) Aug. 13,1998 teaches to synthesize a low molecular weight polymer or oligomer[namely CF₃(C₂F₄)_(n)I or F(C₂F₄)_(n)I] by irradiation of TFE with a UVlamp and heating at 36° C. in the presence of carbon dioxide and of achain transfer agent such as CF₃I or IF.

The main problem in the synthesis of I-telomers and I₂-telomers is thehandling of TFE, which is flammable and explosive; flammability andexplosivity increase with temperature and pressure. Therefore, in thecourse of the synthesis, it is necessary to properly control temperatureand pressure in order not to go beyond critical values. Normally, iftemperature is increased, pressure values must be controlled in such away as not to go beyond 400 kPa at most. This has a negative impact onthe productivity of the process. Indeed, under such conditions, less TFEis available in the liquid phase to react with I₂, which decreases thereaction speed. In principle, speed could be increased by increasing theTFE pressure or the temperature, but this is not possible due to safetyconcerns and to the occurrence of undesired side-reactions (i.e.formation of perfluorocyclobutane, TFE polymerization, formation ofperfluoroalkanes and I₂). Furthermore, the Applicant has observed thatreaction mixtures containing TFE and I₂, which form C₂F₄I₂ and higherlength telomers, are even more flammable and explosive than TFE alone.This is quite surprising, as it was expected that I₂ present in suchmixtures as a result of dissociation of C₂F₄I₂ and higher lengthtelomers would act as a radical scavenger, thereby increasing thestability of the mixture. The same increased risk of flammability andexplosivity is also associated to reaction mixtures containing TFE andCF₃CF₂I used in the synthesis of α-iodoperfluoroalkanes, since they alsogive rise to a certain amount of I₂, which is known to react with TFEgiving rise to C₂F₄I₂.

It is also well known (for example from FERRERO, Fabio, et al. Analysisof the self-heating process of tetrafluoroethylene in a 100-dm3-reactor.Journal of Loss Prevention in the Process Industries. 2012, vol. 25, no.6, p. 1010-1017.) that a further major concern is represented by theMITD (minimum ignition temperature decomposition) of TFE which decreasesby increasing pressure (it decreases from 260° C. at 500 kPa to 230° C.at 1,000 kPa).

EP 702666 A (DU PONT) discloses single-phase, liquid mixtures of TFE andCO₂ which are said to be characterised by reduced explosivity. Thisdocument focuses on the storage and transport of the mixtures anddiscloses only in broad terms that TFE/CO₂ mixtures can be used directlyin TFE polymerization processes or as a diluent/heat sink in chemicalreactions involving TFE. However, this document does not suggest anystabilizing effect of CO₂ on other systems other than TFE.

There is therefore the need to provide a process for the manufacture ofα-iodoperfluoroalkanes and α,ω-diiodoperfluoroalkanes, said processhaving high productivity and, at the same time, increased safety.

An additional drawback encountered in the manufacture of I-telomers andI 2-telomers, e.g. C₄F₉I, C₄F₈I₂, C₆F₁₃I and C₆F₁₂I₂, lies in theformation of an undesired side-product, perfluorocyclobutane (cy-C₄F₈),an inert gas having a boiling point of 6° C. The presence of thisside-product in the reactor decreases the reaction speed. In order toovercome this drawback, it is necessary to purge the reactor, so as toremove cy-C₄F₈, and add further TFE. However, by doing this, not onlycy-C₄F₈ is discharged from the reactor, but also TFE.

JP S53144507 (ASAHI GLASS CO LTD) discloses the preparation of1,4-diiodo perfluorobutane by thermal decomposition of C₂F₄I₂ in thepresence of I₂ and an inert gas. The inert gas has the effect ofreducing the amount of cy-C₄F₈ formed in the course of the process. Thesole inert gas mentioned in this document is nitrogen.

It would thus be desirable to provide a further, safe process for themanufacture of α-iodoperfluoroalkanes and α,ω-diiodoperfluoroalkanesalso allowing to keep to a minimum the amount of cy-C₄F₈ formed in thereaction. It would also be desirable to provide a process that allowsachieving a high productivity of telomers, in particular those having alow molecular weight.

SUMMARY OF INVENTION

The applicant has now found out that α-iodoperfluoroalkanes andα,ω-diiodoperfluoroalkanes of general formula:

A(C₂F₄)_(n)I,  (I)

wherein:A is selected from F, CF₃ and I andn is an integer equal to or higher than 1, with the proviso that, when Ais F,n is an integer higher than 1can be conveniently manufactured by means of a process (or “method”)which comprises heating a mixture [mixture (M1)] containing:

-   -   a compound selected from I₂, CF₃I, CF₃CF₂I and C₂F₄I₂;    -   TFE;    -   and CO₂        at a temperature equal to or higher than 130° C., said mixture        comprising a liquid phase and a gas phase and containing CO₂ in        an amount of at least 18% vol with respect to the gas phase.

It has indeed been found out that the heating of mixture (M1) at atemperature equal to or higher than 130° C. in the presence of CO₂ in anamount of at least 18% vol, preferably of at least 20% vol, providesadvantages in terms of safety, because, in case of accidental ignitionof the gas phase, there is a relevant mitigation of the maximum pressurereached in the reactor.

It has also been found out that the heating of mixture (M1) at atemperature equal to or higher than 130° C. in the presence of CO₂ in anamount of at least 27% provides an additional advantage, since themixture of reaction products obtained from mixture (M1) in the course ofthe process is not explosive.

Preferably, in formula (I) above, A is selected from F and I and n is aninteger higher than 1. More preferably, n ranges from 2 to 4; this rangeis preferred in all preferred embodiments indicated below.

For the sake of clarity, when ranges are indicated in the presentdescription, range ends are always included.

Thus, in a first embodiment, the process allows obtainingα-iodoperfluoroalkanes of formula (Ia):

A(C₂F₄)_(n)I  (Ia)

wherein A is F or CF₃ and n is an integer equal to or higher than 1,with the proviso that, when A is F, n is an integer higher than 1.Preferably, the process allows obtaining α-iodoperfluoroalkanes (Ia*)wherein A is F and n is an integer higher than 1.

In a second embodiment, the process allows obtaining

α,ω-iodoperfluoroalkanes of formula:

I(C₂F₄)_(n)I  (Ib)

wherein n is an integer equal to or higher than 1, preferably higherthan 1.Manufacture of α-iodoperfluoroalkanes

The manufacture of α-iodoperfluoroalkanes of formula (Ia) as definedabove according to the present invention is typically carried out attemperatures ranging from 130° C. to 500° C., the two followingembodiments being preferred.

Process (A)

According to a first preferred embodiment [herein after “process (A)”],the manufacture of α-iodoperfluoroalkanes of formula (Ia) is carried outby heating a mixture (Mia) containing CF₃I or CF₃CF₂I, TFE and CO₂ at atemperature ranging from 170° C. to 250° C., preferably from 190° C. to220° C., while feeding TFE and CO₂ in the course of the process.Typically, CF₃I or CF₃CF₂I are charged in the reactor, the temperatureis raised up to 170° C.-250° C., preferably up to 190° C.-220° C., andTFE and CO₂ are fed in the reactor in the course of the process.

CF₃I and CF₃CF₂I can be manufactured according to methods known in theart, for example as disclosed in U.S. Pat. No. 3,523,140 (MONTEDISONS.P.A.) Aug. 4, 1970, U.S. Pat. No. 3,644,544 (MONTEDISON S.P.A.) Feb.22, 1972, U.S. Pat. No. 4,922,041 (KALI CHEMIE AG) May 1, 1990, and U.S.Pat. No. 7,071,367 (HONEYWELL INT INC) Jun. 15, 2006.

Typically, TFE is added in a molar amount ranging from 0.5 to 3.0 withrespect to CF₃I or CF₃CF₂I.

The process is typically carried out for a time ranging from 1 to 12hours, preferably from 1 to 24 hours, more preferably from 1 to 48hours.

In any case, the amount of TFE and the reaction time will be adjusted bythe skilled person according to the length of the desired telomer; thelonger the reaction time and the higher the TFE amount, the higher thelength of the desired telomer. The formation of the desired telomer canbe monitored on withdrawn samples according to known methods.

The amount of CO₂ is of at least 18%, preferably of at least 20%, morepreferably of at least 27% with respect to the gas phase.

In the course of the process, the pressure in the reactor is monitoredand is not allowed to go beyond 2,500 kPa by purging the reactor.Purging the reactor allows removing any cy-C₄F₈ formed in the course ofthe reaction.

Process (B)

According to a second preferred embodiment [herein after “process (B)”],the manufacture of α-iodoperfluoroalkanes of formula (Ia) is carried outby heating a mixture (M1a) containing CF₃I or CF₃CF₂I, TFE and CO₂ at atemperature ranging from 300° C. to 500° C., preferably from 350° C. to450° C. Typically, CF₃I or CF₃CF₂I are pumped in the reactor attemperature ranging from 300° C. to 500° C., preferably from 350° C. to450° C., while TFE and CO₂ are fed in the reactor in the course of theprocess.

Typically, TFE is added in a molar amount ranging from 0.5 to 3, morepreferably from 0.5 to 1 with respect to CF₃I or CF₃CF₂I. Also in thiscase, the amount of TFE and the reaction time will be adjusted by theskilled person according to the length of the desired telomer.

The amount of CO₂ is of at least 18%, preferably of at least 20%, morepreferably of at least 27% with respect to the gas phase.

In the course of the process, the pressure in the reactor is monitoredand typically kept within a range of 100 kPa and 1,000 kPa.

Usually, both in process (A) and (B), one or more α-iodoperfluoroalkanes(Ia)—typically C₄F₉I and/or C₆F₁₃I in the manufacture ofα-iodoperfluoroalkanes (Ia*)—is/are obtained as a mixture (M2a) withunreacted CF₃I or CF₃OF₂I, TFE and with any C₂F₄I₂ and I₂ possiblyformed in the course of the reaction. Mixture (M2a) may further containcy-C₄F₈ and/or dimeric perfluoroalkanes. The one or moreα-iodoperfluoroalkanes of formula (Ia) or (Ia*) can be isolated byfractionation techniques according to methods known in the art.

Manufacture of α,ω-iodoperfluoroalkanes

The manufacture of a α,ω-iodoperfluoroalkane of formula:

I(C₂F₄)_(n)I  (Ib)

wherein n is 1(1,2-diiodotetrafluoroethane)according to the present invention is typically carried out bycontacting I₂ with TFE and heating at a temperature ranging from 130° C.to 170° C. in the presence of an amount of CO₂ of at least 18%,preferably of at least 20%, more preferably of at least 27% with respectto the gas phase.

The reaction is typically carried out for a time ranging from 1 hr to 6hrs, preferably from 1 hr to 4 hrs, more preferably from 1 hr to 2 hrs.TFE and I₂ are typically used in a molar ratio of about 1:1.

The manufacture of α,ω-iodoperfluoroalkanes of formula:

I(C₂F₄)_(n)I  (Ib)

wherein n is an integer higher than 1according to the invention is typically carried out according to the twofollowing embodiments.

In a first embodiment [herein after “process (C)”], a mixture (M1b)comprising C₂F₄I₂, TFE and CO₂ is heated to a temperature ranging from170° C. to 250° C., preferably of 200° C., while feeding TFE and CO₂ inthe course of the process. Typically, C₂F₄I₂ is fed in the reactor,heated to 170° C.-250° C., preferably at 200° C., and TFE and CO₂ arefed in the reactor in the course of the process.

In a second embodiment [herein after “process (D)”], the heating ofmixture (M1b) is carried out at a temperature in the range of 170°C.-280° C. in the presence of CO₂, without feeding TFE in the course ofthe process.

Mixture (M1b) is typically prepared by contacting TFE with I₂ in thepresence of CO₂, followed by heating at a temperature of 130° C., toprovide a mixture [mixture (M1b)] comprising C₂F₄I₂, TFE and I₂. Mixture(M1b) can be directly subjected to the process or can be submitted to apurification step in order to reduce the amount of I₂ and TFE thereincontained. The purification step can be carried out according to knownmethods.

Process (C)

Typically, process (C) comprises the following steps:

(a1) reacting TFE with I₂ in the presence of CO₂ at a temperature of130° C. to provide a mixture (M1b) of C₂F₄I₂, TFE and I₂;

(a1*) optionally purifying mixture (M1b) to reduce the amount of I₂ andTFE therein contained;

(a2) heating mixture (M1b) at a temperature ranging from 170° C. to 250°C., preferably of 200° C., while feeding TFE and CO₂.

Step (a1) is typically carried out for a time ranging from 1 hr to 6hrs, preferably from 1 hr to 4 hrs, more preferably from 1 hr to 2 hrs.In step (a1), TFE and I₂ are typically used in a molar ratio of about1:1.

Step (a2) is typically carried out for a time ranging from 1 hr to 12hrs, preferably from 1 hr to 24 hrs, more preferably from 1 hr to 48hrs. In this step, TFE is added at a pressure ranging from 1,000 to3,500 kPa. The reaction time and the TFE pressure will be adjusted bythe person skilled in the art according to the length of the desiredtelomer; the longer the reaction time and the higher the TFE pressure,the higher the length of the desired telomer. The formation of thedesired telomer can be monitored on withdrawn samples according to knownmethods.

The amount of CO₂ fed in the reactor in steps (a1) and (a2) is of atleast 18% vol, preferably of at least 20% vol, more preferably of atleast 27% vol with respect to the gas phase of mixture (M1b).

During step (a2), the pressure in the reactor is monitored and kept atvalues not beyond 2,500 kPa by purging the reactor. Purging the reactorallows removing any cy-C₄F₈ formed in the course of the reaction.

Usually, at the end of step (a2), one or more α,ω-diiodoperfluoroalkanesof formula (I), typically C₄F₈I₂ and/or C₆F₁₂I₂, is/are obtained as amixture [mixture (M2b)] with unreacted C₂F₄I₂ and also with TFE and I₂formed by dissociation of C₂F₄I₂. More typically, moreα,ω-diiodoperfluoroalkanes of formula (Ib) are obtained in admixturewith unreacted C₂F₄I₂, TFE and I₂. Mixture (M2b) usually containscy-C₄F₈ as by-product. The one or more α,ω-diiodoperfluoroalkane offormula (Ib) can thus be isolated by submitting mixture (M2b) to apurification step. This purification step can be carried out accordingto known methods, for example as disclosed in JP S51133206 (ASAHI GLASSCO LTD) Nov. 18, 1976.

Process (D)

Process (D) typically comprises the following steps:

(b1) reacting TFE with I₂ in the presence of CO₂ at a temperature of130° C. to provide a mixture (M1b) of C₂F₄I₂, TFE and I₂;

(b1*) optionally purifying mixture (M1b) to reduce the amount of I₂ andTFE therein contained;

(b2) heating mixture (M1b) at a temperature ranging from 170° C. to 280°C., preferably from 200° C. to 250° C., more preferably from 230° C. to250° C. in the presence of CO₂, without feeding TFE.

The reaction time and reagent amounts to be used in step (b1) are thesame as in step (a1).

Step (b2) is typically carried out for a time ranging from 1.5 hr to 24hrs.

The amount of CO₂ fed in the reactor in steps (b1) and (b2) is of atleast 18% vol, preferably of at least 20% vol, more preferably of atleast 27% vol with respect to the gas phase of mixture (M1b).

Process (D) may advantageously comprise an additional step (b2*) whichcomprises reducing the temperature to 130° C. and adding TFE, typicallyin an amount ranging from 10% to 25% wt with respect to the amount ofC₂F₄I₂ in mixture (M1b) before step (b2), in order to quench I₂ formedin the reaction.

Similarly to step (a2), at the end of step (b2) or (b2*), one or moreα,ω-diiodoperfluoroalkanes of formula (Ib), typically C₄F₈I₂ and/orC₆F₁₂I₂, is/are obtained as a mixture [mixture (M2b)] with unreactedC₂F₄I₂ and also with TFE and I₂ formed by dissociation of C₂F₄I₂. Moretypically, more α,ω-diiodoperfluoroalkanes of formula (Ib) are obtainedin admixture with unreacted C₂F₄I₂ and also with TFE and I₂ inequilibrium with C₂F₄I₂. Mixture (M2b) may also contain cy-C₄F₈ asby-product. The one or more α,ω-diiodoperfluoroalkane of formula (Ib)can be thus isolated by submitting mixture (M2b) to a purification step.This purification step can be carried out according to known methods,for example as disclosed in JP S51133206 (ASAHI GLASS CO LTD) Nov. 18,1976.

Product fractions obtained from the purification step that containC₂F₄I₂ and higher length telomers can be conveniently recovered and bere-cycled to steps (a2) or (b2) of process (C) or (D) respectively;thus, such fractions can be used as alternatives or in addition to amixture (M1b) in these embodiments of the invention.

As stated above, the presence of CO₂ in an amount of at least 18% vol,preferably of at least 20% vol, allows increasing the safety of theprocess, because it has a stabilizing effect on the mixture of productsformed in the course of the reaction, in particular on mixtures of C₂F₄and C₂F₄I₂. More specifically, it has been observed that an amount of atleast 18% vol, preferably of at least 20% vol, mitigates the maximumpressure reached in the reactor, while an amount of at least 27% allowsavoiding the risk of explosion.

With respect to process (C), process (D) provides a further advantage,which is that of reducing the amount of undesired cy-C₄F₈ that forms asby-product. While in process (C) an overall weight amount of cy-C₄F₈typically in the range of 35% to 40% with respect to mixture (M2b) isobtained, in process (D) the amount of this side product is below 20%.Process (D) is further advantageous in that purging the reactor duringstep (b2) is not required, which makes the process less troublesome andavoids losses of CO₂ and TFE.

The invention and its advantages will be herein after illustrated ingreater detail in the following experimental section and non-limitingexamples.

Should the disclosure of any patents, patent applications, andpublications which are incorporated herein by reference conflict withthe description of the present application to the extent that it mayrender a term unclear, the present description shall take precedence.

EXPERIMENTAL SECTION Material and Methods 1. General Procedure forProcess (C)

A mixture (M1b) containing a definite amount of C₂F₄I₂ was introduced ina stainless steel reactor and the temperature was raised to 200° C.;thereafter, a TFE and CO₂ mixture (80:20 by vol) was fed in continuousin the reactor. Pressure was adjusted at 2,500 kPa by purging thereactor. At the end of the reaction, the reactor was cooled down to roomtemperature and discharged. In the course of the process, cy-C₄F₈, TFEand CO₂ were purged from the reactor and not recovered.

2. General Procedure for Process (D)

A mixture (M1b) containing a definite amount of C₂F₄I₂ was introduced ina stainless steel reactor and uncondensable substances were evacuatedafter having cooled the reactor with dry-ice. The temperature was raisedto 50° C. and the pressure was equilibrated to 530 kPa with CO₂ whilestirring. Thereafter, the temperature was raised to 235° C., whilepressure rose up to 3,000 kPa, and heating was continued until thecomposition of withdrawn samples revealed an amount of CO₂ of at least30% vol (about 3 hrs).

At this stage, the temperature was lowered to 130° C. and TFE was addedkeeping the reactor at a maximum pressure of 1,500 kPa. Thereafter, thereactor was cooled down to room temperature, purged and discharged.

3. Stability Test

The explosivity of TFE, C₂F₄I₂ and C₄F₈I₂ and of TFE/C₂F₄I₂ mixtures wasevaluated by measuring the pressure at explosion.

The test was performed in a vertically mounted stainless steel autoclave(0.34 L volume and 48 mm diameter).

Pressure at explosion was measured by means of a quick response pressuretransducer (oscillation frequency of the membrane of 10 kHz minimum), anelectronic transducer and a cathode-beam oscillograph. The pressuretransducer was mounted on top of the autoclave.

An ignitor was installed at a distance of 20-30 mm from the bottom ofthe autoclave close to the symmetry axis. A nichrome wire (diameter:0.25 mm; length; 4-6 mm), fused by applying a 150V, was used as theignitor.

An electrically heated nichrome wire spiral (spiral diameter: 10-12 mm;nichrome wire diameter: 1.1 mm; number of turns: 11; spiral length:30-35 mm) was installed at the bottom of the autoclave in order tointensify convection when mixing the tested compounds or mixtures.

Synthesis Examples and Results of Stability Tests Examples 1 and 2Process (C)

Following the procedure disclosed at point 1 of the section “Materialand methods”, Examples 1 and 2 were carried out in a 0.6 L stainlesssteel reactor with the amounts of reagents and conditions reported inTable 1 below.

TABLE 1 Example C2F4I2* TFE CO2 Reaction time (hrs) 1 1,080 g 505 g 132g 47 hrs 2   797 g 434 g  98 g 44 hrs *initial amount of C₂F₄I₂ inmixture (M1b).

At the end of the reaction, mixtures (M2b) were obtained with thecompositions reported in Table 2 below.

TABLE 2 Example C2F4I2 C4F8I2 C6F12I2 C8F16I2 cy-C4F8 1 621 g 365 g 137g 15 g 148 g 2 588 g 189 g  96 g 12 g 131 g

Examples 3 and 4 Process (D)

Following the procedure disclosed at point 2 of the section “Materialand methods”, Examples 3 and 4 were carried out in a 0.6 L stainlesssteel reactor with the amounts of reagents and conditions reported inTable 3 below.

TABLE 3 Reaction time TFE (amount and Example C2F4I2 CO2 (hrs)**addition time) 3 715 g 12 g 6.5 108 g (4 hrs) 4 731 g 12 g 14.5 120 g (4hrs) *initial amount of C₂F₄I₂ in mixture (M1b) * time of reaction isreferred to the end of the heating at 235° C.

At the end of the reaction, mixtures (M2b) were obtained with thecompositions reported in Table 4 below.

TABLE 4 Example C2F4I2 C4F8I2 C6F12I2 C8F16I2 cy-C4F8 3 596 g 128 g 23 g0.3 g 12 g 4 586 g 154 g 37 g   4 g 18 g

Results of Stability Tests

Table 5 below reports the results of stability tests carried out on TFEalone and on mixtures of TFE with C₂F₄I₂ or C₄F₈I₂ at different initialtemperatures and pressures (P₀) in the absence of CO₂. The results areexpressed as the ratio between the maximum pressure reached afterignition (P_(max)) and P₀. For P_(max)/P₀ ratios lower than or equal to1.1 the compound or the mixture is considered stable and not exploding.

The results show (see in particular entries 13-15 compared to entry 3)that mixtures of TFE and C₂F₄I₂ have a higher P_(max)/P₀ ratio than TFE,so they are less safe than TFE alone. The same result was obtained withmixtures of TFE and C₄F₈I₂ (see in particular entry 6).

TABLE 5 N° of P₀ T₀ Concentration (% vol) test (KPa) (° C.) TFE C₂F₄I₂C₄F₈I₂ P_(max)/P₀ 1 1,500 200 100 / / 4.95 2 2,000 200 100 / / 5.1 32,500 200 100 / / 5.35 4 1,500 200 90 / 10 5.5 5 2,000 200 92.5 / 7.55.7 6 2,500 200 94 / 6 6.5 7 1,500 200 45 55 / 5.9 8 1,500 200 95 5 /5.7 9 1,500 200 90 10 / 5.8 10 2,000 200 59 41 / 6.8 11 2,000 200 90 10/ 6.8 12 2,000 200 95 5 / 6.5 13 2,500 200 67 33 / 6.9 14 2,500 200 9010 / 6.9 15 2,500 200 95 5 / 6.7

Table 6 below reports instead the results of stability tests carried outon mixtures of TFE and C₂F₄I₂ at different pressures P₀ and at differentconcentrations of CO₂.

TABLE 6 N° of P₀ T₀ Concentration (% vol) test (KPa) (° C.) TFE C₂F₄I₂CO₂ P_(max)/P₀ 1 1,500 200 85.5 5 9.5 5.6 2 1,500 200 76 5 19 1.4 31,500 200 66.5 5 28.5 1 4 2,500 200 85.5 5 9.5 6.7 5 2,500 200 76 5 191.8 6 2,500 200 66.5 5 28.5 1 7 2,500 200 81 10 9 6.5 8 2,500 200 72 1018 2 9 2,500 200 63 10 27 1 10 2,500 200 40 33 27 1 11 2,500 200 18 5527 1

The results show that, when the concentration of CO₂ in the mixture is18% vol, the P_(max)/P₀ value is significantly lower. The resultsfurther show that, when the concentration of CO₂ in the mixture is 27%vol, no explosion occurs.

1. A process for the manufacture of at least one compound of generalformula (I):A(C₂F₄)_(n)I,  (I) wherein: A is selected from F, CF₃ and I and n is aninteger equal to or higher than 1, with the proviso that, when A is F, nis an integer higher than 1 said process comprising heating a mixture(M1) containing: a compound selected from I₂, CF₃I, CF₃CF₂I and C₂F₄I₂;TFE; and CO₂ at a temperature equal to or higher than 130° C., saidmixture comprising a liquid phase and a gas phase and containing CO₂ inan amount of at least 18% vol with respect to the gas phase.
 2. Theprocess according to claim 1, wherein the amount of CO₂ is of at least20%.
 3. The process according to claim 2, wherein the amount of CO₂ isof at least 27%.
 4. The process according to claim 1, wherein the atleast one compound of general formula (I) is at least oneα-iodoperfluoroalkane of formula (Ia):A(C₂F₄)_(n)I  (Ia) wherein A is F or CF₃ and n is an integer equal to orhigher than 1, with the proviso that, when A is F, n is an integerhigher than
 1. 5. The process according to claim 4, said processcomprising heating a mixture (M1a) containing CF₃I or CF₃CF₂I, TFE andCO₂ at a temperature ranging from 170° C. to 250° C., while feeding TFEand CO₂ in the course of the process.
 6. The process according to claim4, said process comprising heating a mixture (M1a) containing CF₃I orCF₃CF₂I, TFE and CO₂ at a temperature ranging from 300° C. to 500° C.,while feeding TFE and CO₂ in the course of the process.
 7. The processaccording to claim 1, wherein the at least one compound of generalformula (I) is an α,ω-diiodoperfluoroalkane of formula (Ib):A(C₂F₄)_(n)I  (Ib) wherein A is I and n is 1, and wherein said processis carried out by contacting I₂ with TFE and heating at a temperatureranging from 130° C. to 170° C.
 8. The process according to claim 1,wherein the at least one compound of general formula (I) is at least oneα,ω-diiodoperfluoroalkane of formula (Ib):A(C₂F₄)_(n)I  (Ib) wherein A is I and n is an integer higher than
 1. 9.The process according to claim 8, said process comprising heating amixture (M1b) comprising C₂F₄I₂, TFE and CO₂ at a temperature rangingfrom 170° C. to 250° C., while feeding TFE and CO₂ in the course of theprocess.
 10. The process according to claim 9 which comprises thefollowing steps: (a1) reacting TFE with I₂ in the presence of CO₂ at atemperature of 130° C. to provide a mixture (M1b) of C₂F₄I₂, TFE andiodine; (a1*) optionally purifying mixture (M1a) to reduce the amount ofI₂ and TFE therein contained; (a2) heating mixture (M1b) at atemperature ranging from 170° C. to 250° C. while feeding TFE and CO₂ inthe course of the process.
 11. The process according to claim 8, saidprocess comprising heating of a mixture (M1b) comprising C₂F₄I₂, TFE andCO₂ at a temperature ranging from 170° C. to 280° C. in the presence ofCO₂, without feeding TFE in the course of the process.
 12. The processaccording to claim 11 which comprises the following steps: (b1) reactingTFE with I₂ in the presence of CO₂ at a temperature of 130° C. toprovide a mixture (M1b) of C₂F₄I₂, TFE and iodine; (b1*) optionallypurifying mixture (M1b) to reduce the amount of I₂ and TFE thereincontained; (b2) heating mixture (M1) at a temperature ranging from 170°C. to 280° C. in the presence of CO₂, without feeding TFE in the courseof the process.
 13. The process according to claim 12, wherein step (b2)is carried out at a temperature ranging from 200° C. to 250° C.
 14. Theprocess according to claim 13, wherein step (b2) is carried out at atemperature ranging from 230° C. to 250° C.
 15. The process according toclaim 11 further comprising a step (b2*) which comprises reducing thetemperature to 130° C. and adding TFE in an amount ranging from 10% to25% wt with respect to the amount of C₂F₄I₂ in mixture (M1b) before step(b2).
 16. The process according to claim 4, wherein the amount of CO₂ isof at least 20%.
 17. The process according to claim 16, wherein theamount of CO₂ is of at least 27%.
 18. The process according to claim 7,wherein the amount of CO₂ is of at least 20%.
 19. The process accordingto claim 18, wherein the amount of CO₂ is of at least 27%.